The usage of orange pulp activated carbon in the adsorption of 2,4-dichlorophenoxy acetic acid from aqueous solutions.

Among the numerous agrochemicals in use today, the herbicide 2,4-dichlorophenoxy acetic acid (2,4-D), has been widely applied to control broad-leaved weeds in gardens and farming. 2,4-D is commonly preferred because of its low cost and good selectivity. On the other hand, 2,4-D is a poorly biodegradable pollutant. Therefore, this study has focused on the adsorption of 2,4-D from aqueous solutions by using activated carbon. The activated carbon was produced from the orange (Citrus sinensis L.) pulp by chemical activation with zinc chloride. The morphological and chemical characteristics of the activated carbon were investigated by infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and N2-adsorption techniques. Then, the effect of adsorption parameters was researched for 2,4-D adsorption on activated carbon. The experimental data indicated that the adsorption isotherms were well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity was 71.94 mg g-1 at 298 K. The adsorption kinetic of 2,4-D obeys the pseudo-second-order kinetic model. The thermodynamic parameters indicated a feasible, spontaneous and exothermic adsorption. These results show that the prepared activated carbon has good potential for the removal of 2,4-D from aqueous solutions.

FT-NIR spectroscopy and RP-HPLC combined with multivariate analysis reveals differences in plant cell suspension cultures of Thevetia peruviana treated with salicylic acid and methyl jasmonate.

Plant cell suspension culture of T. peruviana is a feasible biotechnological platform for the production of secondary metabolites with anti-proliferative/cytotoxic activity, as phenolic compounds (PC); however, different in in vitro growth conditions may affect the production, demanding strategies to increase the metabolite biosynthesis, as well as the development of sensitive and rapid analytical methods for metabolite monitoring. The Fourier transform near-infrared (FT-NIR) spectroscopy and Reversed-phase high-performance liquid chromatography (RP-HPLC) combined with Multivariate analysis (MVA) were used to detect significant differences in the PC production in cultures treated with two elicitors. The results suggest that the FT-NIR-MVA is useful for discriminating samples according to the treatment, showed significant influence of the PC signal. RP-HPLC-MVA showed that the elicitor effect occurs at 72 h post-elicitation. Detection of dihydroquercetin (maximum concentration = 12.59 mg/L), a flavonoid with anti-cancer properties, is highlighted. Future studies will be aimed at scaling this culture to increase the productivity of dihydroquercetin.

A hybrid process for 2,4-dichlorophenoxy acetic acid herbicidal treatment and its microbial identification by MALDI-TOF mass spectrometry.

The feasibility of coupling photocatalysis and a biological treatment to remove a herbicide - 2,4-dichlorophenoxy acetic acid (2,4-D) - from pure water was examined using batch experiments following three protocols: aerated (A-BR) and non-aerated biodegradation (NA-BR) alone, and intimately combined photodegradation and biodegradation (P-B). In view of a subsequent biological treatment, 15 and 180 min irradiation times were chosen in accordance with spectrophotometric and LC-MS/MS results that indicated the decrease in the COD/TOC ratio during photocatalysis. Pre-treatment led to a quick decrease in concentration of 2,4-D and COD during the biological process: a 78.79 ± 0.30% COD removal and 38.23 ± 3.12% 2,4-D elimination was measured after 5760 min in A-BR, and 80.89 ± 0.81% COD and 81.36 ± 1.37% 2,4-D removal was achieved after 2880 min in P-B. For species identification using matrix-assisted laser desorption/ionization (MALDI)-time of flight (TOF)-TOF/MS equipment, Aeromonas eucrenophila, Stenotrophomonas acidaminiphila, Ralstonia pickettii, Sphingobacterium multivorum and Acinetobacter towneri were identified with high accuracy, and they play important roles in the degradation of 2,4-D.

Monodisperse cobalt(II) based metal-organic coordination polymer beads as a sorbent for solid-phase extraction of chlorophenoxy acid herbicides prior to their quantitation by HPLC.

Metal-organic coordination polymer beads (MOCBs) are described for use as a sorbent for solid-phase extraction of chlorophenoxy herbides. By applying regulation of Co(II) ions, micro-sized monodisperse MOCBs were obtained through the microwave heating. The MOCBs-based method displays excellent extraction efficiency towards chlorophenoxy herbicides, specifically of 2-chlorophenoxyacetic acid, 4-chlorophenoxyacetic acid, 4-chloromethylphenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid and 2-(2,4-dichlorophenoxy)propionic acid. Following extraction, the herbicides were eluted with 8% formic acid in methanol and quantified by HPLC. The method, when applied to analyze spiked cereals, exhibits a wide linear range (from 0.6 to 1000 ng g-1) and low limits of quantification (ranging from 0.10 to 0.25 ng g-1). For a single column, the inter-day and intra-day precisions, expressed as the relative standard deviation are in the range of 2.5-6.8%. The batch-to-batch reproducibility (for n = 3) is <4.6%. For spiked cereal samples, relative recoveries are very good (90.3-102.3%, for n = 4). The extraction efficiency of MOCBs remains unchanged after reusing for 40 times. Graphical abstractSchematic presentation of Co(II)-doped metal-organic coordination polymer beads (Co(II)@MOCB) using for solid-phase extraction (SPE).

Effects of Temperature on Seed Germination of Plantago lanceolata and Management in Carya illinoinensis Production.

Plantago lanceolata L. (buckhorn plantain) is an encroaching winter weed described as one of the most successful noncultivated colonizing species around the world. Control of P. lanceolata in southeastern USA Carya illinoinensis (Wangenh.) K. Koch production has not been studied, nor has the role of temperature on germination using a thermal gradient table. Seed of P. lanceolata collected from a Georgia C. illinoinensis grove were tested for the effects of temperature over time to establish differences in effects on germination using a thermal gradient table. Temperatures ranged from 13.5 to 30.5 °C for 288 h. Cumulative P. lanceolata seed germination was 66% occurring at 17.8 °C at 242 h. Over the 288 h experiment, maximum P. lanceolata germination was 27% occurring at 17.0 °C, 187 h after initiation. Control of P. lanceolata with residual herbicides, or in combination with 2,4-dichlorophenoxyacetic acid (2,4-D) was evaluated in the interrow of C. illinoinensis groves containing Trifolium repens L., and in greenhouse experiments. Pre- and post-emergent herbicides included indaziflam, halosulfuron-methyl, and simazine applied alone, or in combination with 2,4-D in late autumn after P. lanceolata emergence in a C. illinoinensis grove. Indaziflam in combination with 2,4-D controlled P. lanceolata greater than 90% when applied in C. illinoinensis groves and greenhouse experiments. Halosulfuron-methyl and simazine applied alone, or in combination with 2,4-D, provided 67% or less P. lanceolata control in the grove experiments, and 83% or less in greenhouse experiments. Results suggested that herbicide applications should be made during the time when diurnal temperatures are between 15 and 30 °C, while abiding pre-harvest interval restrictions. Post- and pre-emergent herbicides may aid in controlling emerged weeds and reducing further weed emergence during the autumn of that year.

Modelling aerobic biodegradation of atrazine and 2,4-dichlorophenoxy acetic acid by mixed-cultures.

The aim of this work was to study and to model the biodegradation of atrazine and 2,4-dichlorophenoxy acetic acid by aerobic mixed cultures. Slow removal rates were observed when biodegrading atrazine, in spite of the initial concentrations. However, high removal rates were obtained when biodegrading 2,4-D, removing up to 100mg/L in about 2months. Regarding the 2,4-D it must be highlighted that a lag phase appears, being its length proportional to the initial 2,4-D concentration. The biodegradation trends were fitted to a Monod based model and the value of the main parameters determined. In the case of atrazine they were µmax: 0.011 1/d and Y: 0.53g/g and in the case of 2,4-D µmax: 0.071 1/d and Y: 0.44g/g, indicating the higher persistence of atrazine. Once finished the experiments the microbial population was characterized being the major genus Pseudomonas when treating atrazine and Rhodococcus when treating 2,4-D.

Graphene oxide coated with porous iron oxide ribbons for 2, 4-Dichlorophenoxyacetic acid (2,4-D) removal.

Graphene oxide (GO) was prepared from commercially available graphite powder. Porous iron oxide ribbons were grown on the surface of GO by solvothermal process. The prepared GO-Fe3O4 nanocomposites are characterized by FT-IR, XRD, VSM, SEM, TEM, Raman spectroscopy, surface functionality and zero point charge studies. The morphology of the iron oxide ribbons grown on GO is demonstrated with TEM at various magnifications. The presence of magnetite nanoparticles is evident from XRD peaks and the magnetization value is found to be 37.28emu/g. The ratio of intensity of D-peak to G-peak from Raman spectrum is 0.995. The synthesized Graphene oxide-Fe3O4 nanocomposites (GO-Fe3O4) were explored for its surface adsorptive properties by using a model organic compound, 2,4-Dichlorophenoxy acetic acid (2,4-D) from aqueous solution. Batch adsorption studies were performed and the equilibrium data are modelled with Langmuir, Freundlich and Temkin isotherms. The maximum monolayer capacity from Langmuir isotherm is 67.26mg/g. Kinetic studies were also carried out and the studied adsorption process followed pseudo second-order rate equation. Mechanism of the adsorption process is studied by fitting the data with intraparticle diffusion model and Boyd plot. The studied adsorption process is both by film diffusion and intraparticle diffusion.

AuNPs-functionalized PANABA-MWCNTs nanocomposite-based impedimetric immunosensor for 2,4-dichlorophenoxy acetic acid detection.

In this work, we developed an impedimetric label-free immunosensor for the detection of 2,4-Dichlorophenoxy Acetic Acid (2,4-D) herbicide either in standard solution and spiked real samples. For this purpose, we prepared by electropolymerization a conductive polymer poly-(aniline-co-3-aminobenzoic acid) (PANABA) then we immobilized anti-2,4-D antibody onto a nanocomposite AuNPs-PANABA-MWCNTs employing the carboxylic moieties as anchor sites. The nanocomposite was synthesized by electrochemical polymerization of aniline and 3-aminobenzoic acid, in the presence of a dispersion of gold nanoparticles, onto a multi-walled carbon nanotubes-based screen printed electrode. Aniline-based copolymer, modified with the nanomaterials, allowed to enhance the electrode conductivity thus obtaining a more sensitive antigen detection. The impedimetric measurements were carried out by electrochemical impedance spectroscopy (EIS) in faradic condition by using Fe(CN)63-/4- as redox probe. The developed impedimetric immunosensor displayed a wide linearity range towards 2,4-D (1-100ppb), good repeatability (RSD 6%), stability and a LOD (0.3ppb) lower than herbicide emission limits.

Low-dimensional coordination polymeric structures in alkali metal complex salts of the herbicide (2,4-dichlorophenoxy)acetic acid (2,4-D).

The Li, Rb and Cs complexes with the herbicide (2,4-dichlorophenoxy)acetic acid (2,4-D), namely poly[[aqua[µ3-(2,4-dichlorophenoxy)acetato-κ(3)O(1):O(1):O(1')]lithium(I)] dihydrate], {[Li(C8H5Cl2O3)(H2O)]·2H2O}n, (I), poly[µ-aqua-bis[µ3-(2,4-dichlorophenoxy)acetato-κ(4)O(1):O(1'):O(1'),Cl(2)]dirubidium(I)], [Rb2(C8H5Cl2O3)2(H2O)]n, (II), and poly[µ-aqua-bis[µ3-(2,4-dichlorophenoxy)acetato-κ(5)O(1):O(1'):O(1'),O(2),Cl(2)]dicaesium(I)], [Cs2(C8H5Cl2O3)2(H2O)]n, (III), respectively, have been determined and their two-dimensional polymeric structures are described. In (I), the slightly distorted tetrahedral LiO4 coordination involves three carboxylate O-atom donors, of which two are bridging, and a monodentate aqua ligand, together with two water molecules of solvation. Conjoined six-membered ring systems generate a one-dimensional coordination polymeric chain which extends along b and interspecies water O-H...O hydrogen-bonding interactions give the overall two-dimensional layers which lie parallel to (001). In hemihydrate complex (II), the irregular octahedral RbO5Cl coordination about Rb(+) comprises a single bridging water molecule which lies on a twofold rotation axis, a bidentate O(carboxy),Cl-chelate interaction and three bridging carboxylate O-atom bonding interactions from the 2,4-D ligand. A two-dimensional coordination polymeric layer structure lying parallel to (100) is formed through a number of conjoined cyclic bridges, including a centrosymmetric four-membered Rb2O2 ring system with an Rb...Rb separation of 4.3312 (5) Å. The coordinated water molecule forms intralayer aqua-carboxylate O-H...O hydrogen bonds. Complex (III) comprises two crystallographically independent (Z' = 2) irregular CsO6Cl coordination centres, each comprising two O-atom donors (carboxylate and phenoxy) and a ring-substituted Cl-atom donor from the 2,4-D ligand species in a tridentate chelate mode, two O-atom donors from bridging carboxylate groups and one from a bridging water molecule. However, the two 2,4-D ligands are conformationally very dissimilar, with one phenoxyacetate side chain being synclinal and the other being antiperiplanar. The minimum Cs...Cs separation is 4.4463 (5) Å. Structure extension gives coordination polymeric layers which lie parallel to (001) and are stabilized by intralayer water-carboxylate O-H...O hydrogen bonds.

Effect of air desiccation and salt stress factors on in vitro regeneration of rice (Oryza sativa L.).

Enhancement of callus induction and its regeneration efficiency through in vitro techniques has been optimized for 2 abiotic stresses (salt and air desiccation) using 3 rice genotypes viz. BR10, BRRI dhan32 and BRRI dhan47. The highest frequency of callus induction was obtained for BRRI dhan32 (64.44%) in MS medium supplemented with 2, 4-D (2.5 mgL(-1)) and Kin (1.0 mgL(-1)). Different concentrations of NaCl (2.9, 5.9, 8.8 and 11.7 gL(-1)) were used and its effect was recorded on the basis of viability of calli (VC), relative growth rate (RGR), tolerance index (TI) and relative water content (RWC). It was observed that in all cases BRRI dhan47 showed highest performance on tolerance to VC (45.33%), RGR (1.03%), TI (0.20%) and RWC (10.23%) with 11.7 gL(-1) NaCl. Plant regeneration capability was recorded after partial air desiccation pretreatment to calli for 15, 30, 45 and 60 h. In this case BRRI dhan32 gave maximum number of regeneration (76.19%) when 4 weeks old calli were desiccated for 45 h. It was observed that air desiccation was 2-3 folds more effective for enhancing green plantlet regeneration compared to controls. Furthermore, desiccated calli also showed the better capability to survive in NaCl induced abiotic stress; and gave 1.9 fold (88.80%) increased regeneration in 11.7 gL(-1) salt level for BRRI dhan47. Analysis of variance (ANOVA) showed that the genotypes, air desiccation and NaCl had significant effect on plant regeneration at P < 0.01.

Repositioning of 2,4-dichlorophenoxy acetic acid as a potential anti-inflammatory agent: in silico and pharmaceutical formulation study.

2,4-Dichlorophenoxy acetic acid (2,4-D) is a well-known plant auxin which is widely used in plant tissue culture experiments as well as a weed killer and a herbicide. In this study, 2,4-D was rediscovered as a new anti-inflammatory agent through an in silico molecular modeling and docking studies along with drug formulation and in vivo anti-inflammatory inspection. The molecular modeling and docking studies indicated high affinity of 2,4-D toward COX-2 enzyme in a way similar to Ibuprofen, suggesting a higher anti-inflammatory activity. Molecular docking by both MOE 2013.08 and Leadit 2.1.2 revealed excellent binding pattern compared to some of well-known non-steroidal anti-inflammatory drugs. 2,4-D was formulated in different gel bases. In vitro drug release experiments were used to examine the best 2,4-D formula for in vivo studies. In vivo carrageenan-induced hind paw edema inflammatory model in rats was used to test the in silico finding. 2,4-D showed potential in vivo anti-inflammatory activity and significantly reduced the concentration of prostaglandin E2 in hind paw tissues in a way similar to Ibuprofen. These results may open the door to introduce a new anti-inflammatory molecule; especially that 2,4-D is a well-investigated regarding its toxicity and side effect.

Pharmacological potential and conservation prospect of the genus Eucomis (Hyacinthaceae) endemic to southern Africa.

ETHNOPHARMACOLOGICAL RELEVANCE: The genus Eucomis (Hyacinthaceae) consists of 10 species that are extensively used in African traditional medicine. This review is an appraisal of current information on the distribution and morphology, traditional uses, pharmacology, toxicology and approaches devised to enhance the conservation of the genus. METHODS: A systematic and comprehensive literature search using electronic searches such as Scopus, Google Scholar, Web of Science and ethnobotanical books was conducted. RESULTS: Evidence from traditional medicine usage shows wide utilization of this genus for ailments such as respiratory, venereal diseases, rheumatism as well as kidney and bladder infections. Pharmacological screening reported antimicrobial, antiplasmodial, antitumor, cytotoxic, phytotoxic and anti-inflammatory properties. CONCLUSIONS: The potential of the genus Eucomis especially in terms of pharmacology cannot be overemphasized. Apart from the anti-inflammatory properties, the antifungal activity of Eucomis remains a valuable reservoir with potential application in the agriculture sector as a source of an affordable biocontrol agent. Based on the speculated toxic constituents in the genus Eucomis, it will be valuable to conduct detailed toxicological studies. Extensive utilization of members of the genus Eucomis is causing severe strain on wild populations. Although conventional propagation has been relatively effective in the alleviation of the declining status, micropropagation of members may be vital to guarantee the conservation of wild populations.

Comprehensive insights on how 2,4-dichlorophenoxyacetic acid retards senescence in post-harvest citrus fruits using transcriptomic and proteomic approaches.

Auxin-like 2,4-dichlorophenoxyacetic acid (2,4-D), a high-efficiency anti-stalling agent for the post-harvest fresh fruit industry, has had its use restricted due to environmental concerns. However, no other substitutes for 2,4-D are available to the post-harvest industry. Insights into the molecular mechanism underlying the effects of 2,4-D on fruit quality preservation will provide a theoretical basis for exploring new safe and effective anti-stalling agents. This study comprehensively analysed changes in the peel of Olinda Valencia orange [Citrus sinensis (L.) Osbeck] induced by 500 ppm 2,4-D using 'omic'-driven approaches. Transcriptional profiling revealed that transcriptional factor (mainly AP2/ERF, WRKY, and NAC family members), transport, and hormone metabolism genes were over-represented and up-regulated within 24h post-treatment (HPT). Stress defence genes were up-regulated, while cell wall metabolism genes were down-regulated after 48 HPT. However, secondary metabolism genes, especially phenylpropanoid and lignin biosynthesis-related genes, were over-represented at all the time points. Comparative proteomic analysis indicated that the expression of proteins implicated in stress responses (25%), hormone metabolism, and signal transduction (12%) significantly accumulated at the post-transcriptional level. Hormone levels detected by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) showed that abscisic acid, salicylic acid, and 2,4-D significantly increased, while ethylene production (detected by gas chromatography) decreased after 2,4-D treatment. In addition, lignin and water content in the fruit peel also increased and the epicuticle wax ultrastructure was modified. In conclusion, 2,4-D retarded fruit senescence by altering the levels of many endogenous hormones and by improving stress defence capabilities by up-regulating defence-related genes and proteins.

Effect of copper on pro- and antioxidative reactions in radish (Raphanus sativus L.) in vitro and in vivo.

The generation of superoxide radicals, lipid peroxidation (as measured by malone dialdehyde formation) and the activity of selected antioxidant enzymes (superoxide dismutase, catalase, ascorbate peroxidase) were assessed in radish (Raphanus sativus L.), in response to elevated concentrations of copper ions in the culture medium in vitro and in vivo. Experiments were performed on 7-day-old seedlings and 5-week-old calluses grown on media supplemented with CuSO4 in concentrations of 10, 100 and 1000µÐœ. The exposure to elevated Cu concentrations in the medium significantly reduced both callogenesis and the proliferation of radish calluses in vitro. Cu treatment resulted in the increased generation of the superoxide radical (O2(-)) in radish seedlings and calluses indicating the occurrence of oxidative stress in radish cells, whereas the level of lipid peroxidation (LPO) remained unchanged. Both in calluses and in radish seedlings in vivo, the relative level of oxidative stress was maximal at micromolar Cu concentrations and became attenuated with increasing Cu concentrations. Stronger oxidative stress occurred in the radish seedlings in vivo, compared with radish calluses in vitro. The observed lower sensitivity of calluses to Cu-induced oxidative stress and their ability to proliferate upon exposure to Cu concentrations of up to 1000µÐœ demonstrate the potential of in vitro cell-selection to obtain metal-tolerant radish plant lines.

Pesticide exposure and self-reported incident depression among wives in the Agricultural Health Study.

BACKGROUND: Depression in women is a public health problem. Studies have reported positive associations between pesticides and depression, but few studies were prospective or presented results for women separately. OBJECTIVES: We evaluated associations between pesticide exposure and incident depression among farmers' wives in the Agricultural Health Study, a prospective cohort study in Iowa and North Carolina. METHODS: We used data on 16,893 wives who did not report physician-diagnosed depression at enrollment (1993-1997) and who completed a follow-up telephone interview (2005-2010). Among these wives, 1054 reported physician diagnoses of depression at follow-up. We collected information on potential confounders and on ever use of any pesticide, 11 functional and chemical classes of pesticides, and 50 specific pesticides by wives and their husbands via self-administered questionnaires at enrollment. We used inverse probability weighting to adjust for potential confounders and to account for possible selection bias induced by the death or loss of 10,639 wives during follow-up. We used log-binomial regression models to estimate risk ratios and 95% confidence intervals. RESULTS: After weighting for age at enrollment, state of residence, education level, diabetes diagnosis, and drop out, wives' incident depression was positively associated with diagnosed pesticide poisoning, but was not associated with ever using any pesticide. Use of individual pesticides or functional or chemical classes of pesticides was generally not associated with wives' depression. Among wives who never used pesticides, husbands' ever use of individual pesticides or functional or chemical classes of pesticides was generally not associated with wives' incident depression. CONCLUSIONS: Our study adds further evidence that high level pesticide exposure, such as pesticide poisoning, is associated with increased risk of depression and sets a lower bound on the level of exposure related to depression, thereby providing reassurance that the moderate levels of pesticide exposure experienced by farmers' wives likely do not increase risk.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing ß-Cyclodextrin.

Urethane copolymer sorbent materials that incorporate ß-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 10¹ m²/g), CDI-X copolymers (< 10¹ m²/g), and granular activated carbon (GAC ~10³ m²/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

Retention Behavior of Acid Drugs in Microemulsion Liquid Chromatography / 分析化学

The retention mechanism of acid drugs such as naproxen, ibuprofen, diclofenac, phenylalanine and 2,4-dichlorophenoxy acetic acid in microemulsion liquid chromatography has been discussed.The reten tion modeling between capacity factors (k') of acid drugs in microemulsion liquid chromatography and concen tration of surfactant, cosurfactant and lipophilic organic solvent and pH value was set.The results showed the effect of change of concentration of surfactant, cosurfactant and lipophilic organic solvent and pH value on capacity factors of acid drugs in microemulsion liquid chromatography was fully consistent with the theoretical modeling.The retention modeling can better reflect the effect of composition of microemulsion solution and pH value on retention behavior of acid drugs in microemulsion liquid chromatography.